Phosphorus containing aromatic amino polyols

ABSTRACT

A class of Mannich condensates containing phosphorus prepared by reacting a phenol with formaldehyde and a primay amine, and then reacting the product with formaldehyde and a dialkyl phosphite. Useful applications include use as a fire retardant additive in polyurethane foams.

FIELD OF THE INVENTION

This invention pertains to the introduction of phosphorus into aromatic amino polyols by the Mannich reaction and its use as a fire retardant additive in polyurethane foams.

DESCRIPTION OF THE RELATED ART

The Mannich reaction involves the reaction of an acidic hydrogen with formaldehyde and an amino base. U.S. Pat. No. 4,310,592 to Schmitz illustrates the manner in which the Mannich reaction can be used to prepare useful products. The patent teaches that when an aliphatic amine and formaldehyde are reacted with phenol, the reaction yields predominantly an ortho substituted Mannich base. According to the patent, the reaction proceeds by the following general equation: ##STR1## wherein R is an alkyl radical containing from about 12 to 22 carbon atoms.

U.S. Pat. No. 3,076,010 discloses that when instead of a phenol, a dialkyl phosphite is reacted with an aldehyde or ketone and a dialkanolamine, a compound is formed which may be represented by the formula: ##STR2## in which R and R' may be the same or different alkyl or haloalkyl radicals, R² and R³ may be the same or different lower alkylene radicals and R₄ is hydrogen or an alkyl radical. U.S. Pat. No. 3,076,010 instructs that these compounds may be made according to the general reaction: ##STR3## wherein R, R', R², R³ and R⁴ are defined as above.

U.S. Pat. No. 4,052,487 represents an improvement on the teachings of U.S. Pat. No. 3,076,010 by disclosing the development of a diol phosphonate having the general formula: ##STR4## in which R is an alkyl group with 1 to 4 carbon atoms, R² is hydrogen, a methyl or an ethyl group, and R' is --CH₂ --CH₂ --CH₂ -- or ##STR5## This diol-phosphonate was found useful as a flame-proofing additive in polyurethane foams.

The invention disclosed herein combines elements of the two reactions disclosed in U.S. Pat. Nos. 4,310,592 and 3,076,010 to produce a new class of Mannich condensates.

SUMMARY OF THE INVENTION

The invention is a compound comprising a phenol which is substituted by a phosphorus containing structure having the formula: ##STR6## in which R is hydrogen, an alkyl, alkanol or polyoxyalkylene group, and R' is an alkyl group.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The Mannich reaction involves the reaction of an acidic hydrogen with formaldehyde and an amino base. The phosphorus-hydrogen bond is acidic in dialkyl phosphites and will undergo the Mannich reaction with an N--H bond in the presence of formaldehyde. When phosphorus is introduced into aromatic amino polyols by the Mannich reaction, the resulting products have a variety of uses; for example, fire retardants for rigid urethane foams and epoxy plastics, lubricating additives, gasoline wear-inhibiting additives, corrosion inhibitors and surfactants, and may also be propoxylated to other useful polyols for urethanes.

These compounds may be prepared by a Mannich reaction between a phenol, formaldehyde, a primary amine and a dialkyl phosphite as illustrated by the following reaction sequence: ##STR7## in which R is hydrogen, an alkyl, alkanol or polyoxyalkylene group, and R' is an alkyl group. It is preferred that R is an alkanol group. Especially preferred is --CH₂ --CH₂ OH. A preferred compound may be represented by the following structure: ##STR8## Some useful phenols include phenol, nonylphenol, isopropylphenol, cresol, dodecylphenol or Bisphenol A. It is preferred that the phosphite used be dimethyl phosphite or diethyl phosphite.

The conditions within which this invention is useful include a temperature range of 15° to 150° C. and a pressure range of 1 to 200 atmospheres. It is preferred that the reaction be run at a pressure of 1 atmosphere.

Though the products of this invention have a number of applications, of particular interest is their application as fire retarding agents for plastics. Those products which contain several hydroxy groups are especially suitable as fire retardants for urethane foams. This invention and its application as a fire retardant for urethane foams will be further illustrated by the following non-limiting examples.

EXAMPLE 1

To a 1 liter, three-necked flask equipped with a stirrer, thermometer and dropping funnel were added 220 g of nonylphenol (1.0 moles) and 61 g of monoethanolamine. The mixture was cooled to 15° C. and 81.1 g of formalin (1.0 moles) were added slowly while keeping the temperature at 15°-20° C. After all the formalin was added, the mixture was stirred for 30 minutes and then heated to 90° C. and held at this temperature under about 20 mm pressure for two hours. The product weighed 291.5 g and analysis indicated 50% of ortho hydrogens on nonylphenol underwent the Mannich reaction.

To 100 g of the product described above was added 47.13 g of diethyl phosphite (0.341 moles). Then 27.65 g of formalin (0.341 moles) was added and the temperature allowed to rise to 55° C. The contents were heated to 90° C. and held at 90°-108° C. for five hours at full water aspirator reduced pressure while removing water. The final product weighed 142.2 g and was a thick, light brown liquid. It had a hydroxyl number of 78 and a total amine content of 1.85 meq/g.

The procedure described above illustrates in general the technique used in this work. Specific examples are described in Tables I and II using nonylphenol, phenol and Bisphenol A. A wide variety of amines were used. Diethyl phosphite was used in all runs shown except 11 of Table I in which dimethyl phosphite was used.

                                      TABLE I                                      __________________________________________________________________________     REACTIONS OF DIETHYL PHOSPHITE, AMINES,                                        FORMALDEHYDE AND NONYLPHENOL                                                   Nonyl-               Analysis Reaction                                                                               Reaction                                    phenol,                                                                            Amines,                                                                              CH.sub.2 O,                                                                        DEP,                                                                               Total                                                                              Hydroxyl                                                                            Stage #1                                                                               Stage #2                                 Ex.                                                                               Moles                                                                              Moles Moles                                                                              Moles                                                                              Amine                                                                              Number                                                                              Hrs-Temp., °C.                                                                  Hrs-Temp., °C.                    __________________________________________________________________________     1  0.34                                                                               MEA   0.34                                                                               0.34                                                                               1.85                                                                               78   2   110 5   100                                         0.34                                                                    2  0.52                                                                               DGA   0.50                                                                               0.5 1.81                                                                               236  1   110 4   110                                         0.5                                                                     3  0.14                                                                               M-600 0.28                                                                               0.28                                                                               1.12                                                                               57   --  --  3   100                                         0.28                                                                    4  0.07                                                                               M-1000                                                                               0.13                                                                               0.13                                                                               0.56                                                                               23   --  --  3   110                                         0.13                                                                    5  0.17                                                                               M-300 0.33                                                                               0.33                                                                               1.62                                                                               34   3   110 3   110                                         0.33                                                                    6  0.25                                                                               D-400 0.50                                                                               0.50                                                                               2.49                                                                               150  4   110 4   110                                         0.5                                                                     7  0.25                                                                               D-400 0.50                                                                               0.50                                                                               2.14                                                                               119  4   110 4   110                                         0.5                                                                     8  0.25                                                                               ED-600                                                                               0.50                                                                               0.50                                                                               2.01                                                                               123  8   110 4   110                                         0.5                                                                     9  0.07                                                                               T.sub.3 EDMA                                                                         0.13                                                                               0.13                                                                               2.30                                                                               207  3   110 4   110                                         0.13                                                                    10 0.1 T.sub.4 EGMA                                                                         0.20                                                                               0.20                                                                               5.22                                                                               192  3   110 3   110                                         0.20                                                                    11 0.14                                                                               M-600 0.28                                                                               DMP 1.05                                                                               61   2   110 2   110                                         0.28      0.28                                                          12 0.5 DGA   0.93                                                                               0.93                                                                               2.50                                                                               200  3   110 3   110                                         1.0                                                                     13 0.5 MEA   0.92                                                                               0.92                                                                               2.23                                                                               169  3   110 3   110                                         1.0                                                                     14 0.5 M-360 0.97                                                                               0.97                                                                               1.36                                                                               80   3   110 3   110                                         1.0                                                                     __________________________________________________________________________      Monoethanolamine (MEA) = NH.sub.2 CH.sub.2 CH.sub.2 OH                         DIGLYCOLAMINE ® Agent = NH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2      OH                                                                             ##STR9##                                                                       ##STR10##                                                                      ##STR11##                                                                      ##STR12##                                                                      ##STR13##                                                                      T.sub.3 EGMA = NH.sub.2(CH.sub.2 CH.sub.2 O).sub.3 H                           T.sub.4 EGMA = NH.sub.2(CH.sub.2 CH.sub.2 O).sub.4 H                           ##STR14##                                                                      All amines obtained from Texaco Chemical Company.                        

                                      TABLE II                                     __________________________________________________________________________     REACTIONS OF DIETHYL PHOSPHITE, AMINES,                                        FORMALDEHYDE AND PHENOL                                                                                      Reaction                                                                             Reaction                                                        Analysis Stage #1                                                                             Stage #2                                      Phenol,                                                                             Amines,                                                                             CH.sub.2 O,                                                                        DEP,                                                                               Total                                                                              Hydroxyl                                                                            Hrs-Temp.,                                                                           Hrs-Temp.,                                 Ex.                                                                               Moles                                                                               Moles                                                                               Moles                                                                              Moles                                                                              Amine                                                                              Number                                                                              °C.                                                                           °C.                                 __________________________________________________________________________     1  1.0  M-300                                                                               0.33                                                                               0.33                                                                               1.86                                                                               105  3  110                                                                               5  110                                             0.33                                                                   2  0.5  M-300                                                                               1.0 1.0 2.0 128  3  110                                                                               5  110                                             1.0                                                                    3  0.5  M-1000                                                                              0.5 0.5 0.75                                                                                48  4  110                                                                               5  110                                             0.5                                                                    4  0.5  M-600                                                                               1.0 1.0 1.18                                                                                83  4  110                                                                               4  110                                             1.0                                                                    5  1.0  M-600                                                                               1.0 1.0 1.17                                                                                83  3  110                                                                               4  110                                             1.0                                                                    6  0.25 M-1000                                                                              0.5 0.5 0.71                                                                                36  9  110                                                                               6  110                                             0.5                                                                    7  0.25 ED-600                                                                              0.5 0.5 2.13                                                                               132  8  110                                                                               5  110                                             0.5                                                                    8  0.5  MEA  1.5 1.5 3.15                                                                               176  3  110                                                                               3  110                                             1.5                                                                    9  0.25 D-400                                                                               0.46                                                                               0.46                                                                               2.78                                                                               171  3  110                                                                               4  110                                             0.5                                                                    __________________________________________________________________________

                                      TABLE III                                    __________________________________________________________________________     REACTIONS OF DIETHYL PHOSPHITE, AMINES,                                        FORMALDEHYDE AND BISPHENOL A                                                                                  Reaction                                                                             Reaction                                                        Analysis Stage #1                                                                             Stage #2                                     BPA,                                                                               Amines,                                                                               CH.sub.2 O,                                                                        DEP,                                                                               Total                                                                              Hydroxyl                                                                            Hrs-Temp.,                                                                           Hrs-Temp.,                                Ex.                                                                               Moles                                                                              Moles  Moles                                                                              Moles                                                                              Amine                                                                              Number                                                                              °C.                                                                           °C.                                __________________________________________________________________________     1  0.16                                                                               M-300  0.33                                                                               0.33                                                                               1.85                                                                               30   3  110                                                                               3  110                                           0.33                                                                    2  0.17                                                                               M-600  0.33                                                                               0.33                                                                               1.14                                                                               80   3  110                                                                               3  110                                           0.33                                                                    3  0.25                                                                               ED-600 0.5 0.5 --  --   5  110                                                                               Polymer                                          0.5                                                                     4  0.03                                                                               M-1000 0.06                                                                               0.06                                                                               --  --   3  110                                                                               Liquid 50° C.                             0.03                                                                           M-300 (0.03)                                                            __________________________________________________________________________

EXAMPLE 2

Several of the products prepared in this invention were tested in rigid polyurethane and polyurethane-isocyanurate foam formulations. The foams were prepared by standard one-shot, free-rise techniques. Formulation components were mixed at 2700 rpm and poured into an 8"×8"×12" (600 g pour) open mold and allowed to rise. The resulting foams were allowed to stand at ambient conditions for at least three days before determination of physical properties.

It was found that the use of the products of this invention adds fire retardant properties to the foams, improves both insulation values (K-factor) and compression strength, and results in higher heat distortion temperatures. The improvement of foam physical properties also occurs in isocyanurate foams, and, in addition, the friability of the foams is improved. It was found that foams made using DIGLYCOLAMINE® (DGA) agent were easiest to work with and were conveniently prepared.

Formulations, reaction profiles and foam physical properties are detailed in the following table for various comparative and inventive examples.

    __________________________________________________________________________     EXPERIMENTAL FIRE RETARDANT EVALUATIONS                                        __________________________________________________________________________                                                       Nonylphenol/                                                      Nonylphenol/MEA Based                                                                       DGA Based                                                         (See Table I)                                                                               (See Table I)                                  Comparative Examples                                                                              Ex. Ex.  Ex. Ex.                                                                               Ex.                       Fire Retardant    --  AB-80.sup.1                                                                        -- AB-80                                                                              AB-80                                                                              1   13   13  2  2                         __________________________________________________________________________     Formulation, pbw                                                               THANOL ® R-350-X.sup.2 (OH = 526)                                                            37.3                                                                               35.1                                                                               24.6                                                                              23.2                                                                               --  34.7                                                                               34.3 22.7                                                                               34.0                                                                              22.5                      TERATE ® 203.sup.3 (OH = 309)                                                                --  --  16.4                                                                              15.4                                                                               --  --  --   15.0                                                                               -- 14.9                      R-440.sup.4 (OH = 258)                                                                           --  --  -- --  --  --  --   --  -- --                        R-440.sup.4 (OH = 252)                                                                           --  --  -- --  28.9                                                                               --  --   --                               Fire Retardant    --  5.0 -- 5.0 5.0 5.0 4.9  4.9 4.8                                                                               4.8                       DC-193.sup.5      0.5 0.5 0.5                                                                               0.5 0.5 0.5 0.5  0.5 0.5                                                                               0.5                       R-11A.sup.6       13.0                                                                               13.0                                                                               13.0                                                                              13.0                                                                               12.0                                                                               13.0                                                                               13.0 13.0                                                                               13.0                                                                              13.0                      Water             --  --  0.3                                                                               0.3 --  --  --   0.3 -- 0.3                       FOMREZ ® UL-32.sup.7                                                                         --  --  0.01                                                                              0.01                                                                               --  --  --   0.01                                                                               -- 0.01                      T-45.sup.8        --  --  -- --  1.5 --  --   --  -- --                        MONDUR ® MR.sup.9                                                                            49.2                                                                               46.4                                                                               45.2                                                                              42.6                                                                               52.1                                                                               --  --   --                               PAPI ® 27.sup.10                                                                             --  --  -- --  --  46.8                                                                               47.3 43.6                                                                               47.7                                                                              44.0                      Index             1.05                                                                               1.05                                                                               1.05                                                                              1.05                                                                               3.0 1.05                                                                               1.05 1.05                                                                               1.05                                                                              1.05                      Reaction Profile                                                               Times (sec), mixing                                                                              15  15  12 12  3   15  15   12  15 12                        Times (sec), cream                                                                               25  24  17 20  8   28  28   21  25 21                        Times (sec), gel  78  86  52 70  21  99  98   71  92 73                        Times (sec), tack free                                                                           106 110 81 94  32  117 124  113 108                                                                               102                       Times (sec), rise 187 186 139                                                                               153 64  199 210  180 251                                                                               198                       Initial Surface Fri-                                                                             None                                                                               None                                                                               Yes                                                                               None                                                                               Yes None                                                                               None Yes None                                                                              None                      ability                                                                        Foam appearance   Good                                                                               Good                                                                               Fair                                                                              Good                                                                               Good                                                                               Good                                                                               Good Good                                                                               Good                                                                              Good                      Physical Properties                                                            Density, pcf      1.96                                                                               1.99                                                                               1.65                                                                              1.72                                                                               1.86                                                                               1.85                                                                               1.92 1.63                                                                               1.97                                                                              1.68                      K-factor          0.118                                                                              0.119                                                                              0.112                                                                             0.128                                                                              0.117                                                                              0.111                                                                              0.115                                                                               0.112                                                                              0.111                                                                             0.112                     Compressive strength,                                                          psi, with rise    47.57                                                                              41.92                                                                              40.81                                                                             38.31                                                                              38.41                                                                              46.89                                                                              48.61                                                                               37.39                                                                              41.79                                                                             31.66                     against rise      16.58                                                                              14.90                                                                              10.54                                                                             10.51                                                                              11.05                                                                              15.82                                                                              14.89                                                                               10.15                                                                              12.52                                                                             7.36                      Heat distortion, °C.                                                                      158 144 136                                                                               115 191 137 142  131 154                                                                               136                       Closed cells, %   92.25                                                                              91.51                                                                              92.55                                                                             91.43                                                                              91.30                                                                              91.10                                                                              93.07                                                                               92.21                                                                              92.59                                                                             92.94                     Friability, % wt. 6.63                                                                               5.88                                                                               2.07                                                                              2.43                                                                               24.90                                                                              5.64                                                                               7.62 4.93                                                                               6.27                                                                              3.73                      loss, 10 min                                                                   ASTM 1692 Burn,   2.57                                                                               1.64                                                                               2.27                                                                              1.82                                                                               1.19                                                                               3.07                                                                               2.06 2.86                                                                               1.86                                                                              1.76                      in/min (BHA)                                                                   Butler Chimney Test                                                            Flame height, in. >11 >11 >11                                                                               >11 4.33                                                                               >11 >11  >11 >11                                                                               >11                       Sec. to extinguish                                                                               26  20  25 14  12.33                                                                              24  19   17  23 16                        % wt. retained    20.1                                                                               64.3                                                                               31.4                                                                              68.7                                                                               93.2                                                                               36.2                                                                               52.0 54.7                                                                               43.3                                                                              58.0                      Dimensional Stability                                                          158° F., 100% R-H                                                       1 week                                                                              ΔV     +2.7                                                                               +8.4                                                                               +2.9                                                                              +16.5                                                                              +5.3                                                                               +2.9                                                                               +3.2 +4.1                                                                               +4.3                                                                              +4.1                           ΔW     -0.3                                                                               -0.7                                                                               -0.6                                                                              -1.0                                                                               -1.9                                                                               +0.3                                                                               +0.2 +0.1                                                                               -0.4                                                                              -0.6                           ΔL     +1.8                                                                               +5.4                                                                               +2.2                                                                              +11.9                                                                              +3.4                                                                               +2.5                                                                               +2.2 +3.3                                                                               +2.5                                                                              +2.4                      4 weeks                                                                             ΔV     +5.4                                                                               +16.8                                                                              +7.7                                                                              +42.5                                                                              +9.8                                                                               +5.4                                                                               +6.1 +7.7                                                                               +8.4                                                                              +10.3                          ΔW     -0.3                                                                               -1.2                                                                               -0.6                                                                              -2.8                                                                               -3.1                                                                               +0.4                                                                               +0.2 0.0 0.0                                                                               -0.1                           ΔL     +3.4                                                                               +9.9                                                                               +5.1                                                                              +23.0                                                                              +5.9                                                                               +4.6                                                                               +4.0 +5.7                                                                               +5.0                                                                              +5.9                      __________________________________________________________________________                       Nonylphenol/DGA                                                                            Nonylphenol/M-300 Based                                                                      Bispenol A/M-300 Based                               Based (See Table I)                                                                        (See Table I) (See Table II)                                       Ex. Ex. Ex  Ex.  Ex.  Ex. Ex. Ex.  Ex.                       Fire Retardant    12  12  12  5    5    5   1   1    1                         __________________________________________________________________________     Formulation, pbw                                                               THANOL ® R-350-X.sup.2 (OH = 526)                                                            34.1                                                                               22.5                                                                               --  34.9 23.1 --  35.0                                                                               23.1 --                        TERATE ® 203.sup.3 (OH = 309)                                                                --  15.0                                                                               --  --   15.3 --  --  15.3 --                        R-440.sup.4 (OH = 258)                                                                           --  --  26.4                                                                               --   --   28.2                                                                               --  --   28.3                      R-440.sup.4 (OH = 252)                                                         Fire Retardant    4.9 4.9 4.6 5.0  5.0  4.9 5.0 5.0  4.9                       DC-193.sup.5      0.5 0.5 0.5 0.5  0.5  0.5 0.5 0.5  0.5                       R-11A.sup.6       13.0                                                                               13.0                                                                               12.0                                                                               13.0 13.0 12.0                                                                               13.0                                                                               13.0 12.0                      Water             --  0.3 --  --   0.3  --  --  0.3  --                        FOMREZ ® UL-32.sup.7                                                                         --  0.01                                                                               --  --   0.01 --  --  0.01 --                        T-45.sup.8        --  --  1.0 --   --   1.0 --  --   1.0                       MONDUR ® MR.sup.9                                                          PAPI ® 27.sup.10                                                                             47.5                                                                               43.8                                                                               55.5                                                                               46.6 42.8 53.4                                                                               46.5                                                                               42.8 53.3                      Index             1.05                                                                               1.05                                                                               3.0 1.05 1.05 3.0 1.05                                                                               1.05 3.0                       Reaction Profile                                                               Times (sec), mixing                                                                              15  12  6   15   12   6   15  12   6                         Times (sec), cream                                                                               27  21  14  25   17   13  26  17   15                        Times (sec), gel  92  71  46  97   69   49  97  65   49                        Times (sec), tack free                                                                           112 91  56  128  95   93  123 99   77                        Times (sec), rise 223 202 134 211  165  152 219 166  156                       Initial Surface Fri-                                                                             None                                                                               None                                                                               None                                                                               None None Yes None                                                                               None Yes                       ability                                                                        Foam appearance   Good                                                                               Good                                                                               Good                                                                               Good Good Good                                                                               Good                                                                               Good Good                      Physical Properties                                                            Density, pcf      1.97                                                                               1.70                                                                               1.84                                                                               2.01 1.68 1.96                                                                               2.00                                                                               1.68 1.99                      K-factor          0.114                                                                              0.110                                                                              0.110                                                                              0.121                                                                               0.118                                                                               0.122                                                                              0.118                                                                              0.117                                                                               0.119                     Compressive strength,                                                          psi, with rise    43.80                                                                              34.47                                                                              33.12                                                                              41.46                                                                               30.69                                                                               35.03                                                                              44.26                                                                              35.26                                                                               40.64                     against rise      12.52                                                                              8.25                                                                               9.64                                                                               14.93                                                                               10.33                                                                               13.68                                                                              15.18                                                                              10.59                                                                               15.27                     Heat distortion, °C.                                                                      145 127 207 144  124  212 153 123  204                       Closed cells,     93.24                                                                              93.22                                                                              93.17                                                                              92.14                                                                               93.10                                                                               92.67                                                                              92.10                                                                              93.27                                                                               91.88                     Friability, % wt. 5.38                                                                               4.24                                                                               4.46                                                                               5.79 2.32 6.42                                                                               7.43                                                                               2.30 11.88                     loss, 10 min                                                                   ASTM 1692 Burn,   1.87                                                                               2.14                                                                               1.81                                                                               1.83 2.15 1.33                                                                               2.20                                                                               2.64 1.79                      in/min (BHA)                                                                   Butler Chimney Test                                                            Flame height, in. >11 >11 7.67                                                                               >11  >11  9.0 >11 >11  9.75                      Sec. to extinguish                                                                               21  14  12  32   24   12  23  25   11.75                     % wt. retained    55.4                                                                               64.8                                                                               84.4                                                                               49.5 50.9 84.6                                                                               47.8                                                                               51.5 88.8                      Dimensional Stability                                                          158° F., 100% R-H                                                       1 week                                                                              ΔV     +3.6                                                                              +7.0 +4.6                                                                              +7.7 +16.7                                                                               +5.0                                                                               +5.6 +10.3                                                                               +3.7                           ΔW     -0.3                                                                              -0.4 -1.9                                                                              -0.9 -1.0 -1.4                                                                               -0.6 -0.2 -1.8                           ΔL     +2.4                                                                              +4.6 +3.2                                                                              +4.7 +10.1                                                                               +3.4                                                                               +3.4 +7.1 +3.5                      4 weeks                                                                             ΔV     +7.7                                                                              +17.5                                                                               +8.7                                                                              +14.1                                                                               +35.5                                                                               +8.4                                                                               +10.6                                                                               +24.8                                                                               +6.9                           ΔW     -0.2                                                                              0.0  -2.0                                                                              -1.3 -2.0 -2.0                                                                               -0.7 -0.7 -2.6                           ΔL     +4.7                                                                              +10.3                                                                               +5.9                                                                              +8.6 +18.0                                                                               +5.6                                                                               +6.4 +15.0                                                                               +5.7                      __________________________________________________________________________                                        Phenol/M-300 Based                                                             (See Table II)                                                                 Ex. Ex. Ex.                                                                               Ex. Ex. Ex.                                       Fire Retardant    1   1   1  2   2   2                        __________________________________________________________________________                      Formulation, pbw                                                               THANOL ® R-350-X.sup.2 (OH = 526)                                                            34.6                                                                               22.9                                                                               -- 34.5                                                                               22.8                                                                               --                                        TERATE ® 203.sup.3 (OH = 309)                                                                --  15.2                                                                               -- --  15.1                                                                               --                                        R-440.sup.4 (OH = 258)                                                                           --  --  27.4                                                                              --  --  27.2                                      R-440.sup.4 (OH = 252)                                                         Fire Retardant    4.9 4.9 4.8                                                                               4.9 4.9 4.7                                       DC-193.sup.5      0.5 0.5 0.5                                                                               0.5 0.5 0.5                                       R-11A.sup.6       13.0                                                                               13.0                                                                               12.0                                                                              13.0                                                                               13.0                                                                               12.0                                      Water             --  0.3 -- --  0.3 --                                        FOMREZ ® UL-32.sup.7                                                                         --  0.01                                                                               -- --  0.01                                                                               --                                        T-45.sup.8        --  --  1.0                                                                               --  --  1.0                                       MONDUR ® MR.sup.9                                                          PAPI ® 27.sup.10                                                                             47.0                                                                               43.2                                                                               54.3                                                                              47.1                                                                               43.4                                                                               54.6                                      Index             1.05                                                                               1.05                                                                               3.0                                                                               1.05                                                                               1.05                                                                               3.0                                       Reaction Profile                                                               Times (sec), mixing                                                                              15  12  6  15  12  6                                         Times (sec), cream                                                                               27  18  15 18  13  14                                        Times (sec), gel  100 74  72 87  68  64                                        Times (sec), tack free                                                                           137 104 98 106 98  108                                       Times (sec), rise 216 162 150                                                                               184 149 155                                       Initial Surface Fri-                                                                             None                                                                               None                                                                               Yes                                                                               None                                                                               None                                                                               Yes                                       ability                                                                        Foam appearance   Good                                                                               Good                                                                               Fair                                                                              Good                                                                               Good                                                                               Good                                      Physical Properties                                                            Density, pcf      2.04                                                                               1.69                                                                               2.04                                                                              2.00                                                                               1.65                                                                               2.00                                      K-factor          0.111                                                                              0.113                                                                              0.114                                                                             0.112                                                                              0.113                                                                              0.114                                     Compressive strength,                                                          psi, with rise    46.12                                                                              34.98                                                                              34.64                                                                             45.20                                                                              33.29                                                                              34.51                                     against rise      16.67                                                                              10.89                                                                              15.09                                                                             15.92                                                                              10.05                                                                              13.94                                     Heat distortion, °C.                                                                      148 119 210                                                                               148 122 209                                       Closed cells,     91.89                                                                              92.81                                                                              92.60                                                                             91.98                                                                              93.01                                                                              92.70                                     Friability, % wt. 16.03                                                                              3.07                                                                               7.57                                                                              6.67                                                                               1.98                                                                               5.03                                      loss, 10 min                                                                   ASTM 1692 Burn,   2.05                                                                               2.41                                                                               1.79                                                                              1.87                                                                               2.57                                                                               1.75                                      in/min (BHA)                                                                   Butler Chimney Test                                                            Flame height, in. >11 >11 10.0                                                                              >11 >11 >11                                       Sec. to extinguish                                                                               28  13  13 28  22  12                                        % wt. retained    45.3                                                                               65.2                                                                               85.6                                                                              44.2                                                                               53.6                                                                               83.3                                      Dimensional Stability                                                          158° F., 100% R-H                                                       1 week                                                                              ΔV     +4.4                                                                               +13.6                                                                              +5.8                                                                              +4.6                                                                               +10.8                                                                              +4.9                                           ΔW     +0.2                                                                               -0.3                                                                               -1.8                                                                              +0.1                                                                               -0.4                                                                               -1.5                                           ΔL     +2.7                                                                               +8.9                                                                               +5.6                                                                              +3.0                                                                               +7.2                                                                               +4.2                                      4 weeks                                                                             ΔV     +10.1                                                                              +34.0                                                                              +9.4                                                                              +11.1                                                                              +30.0                                                                              +8.7                                           Δ W    +0.1                                                                               -0.9                                                                               -2.4                                                                              0.0 -0.9                                                                               -2.2                                           ΔL     +5.9                                                                               +18.7                                                                              +8.1                                                                              +6.7                                                                               +17.3                                                                              +6.6                     __________________________________________________________________________      .sup.1 ANTIBLAZE ® 80  Tris(2-chloropropyl phosphate) fire retardant       made by Mobil Chemical Co.                                                     .sup.2 Aromatic amino polyol sold by Texaco Chemical Co.                       .sup.3 Aromatic polyester polyol sold by Hercules, Inc.                        .sup.4 Experimental aromatic polyester polyol made by Texaco Chemical Co.      .sup.5 Silicone surfactant sold by Dow-Corning.                                .sup.6 Trichlorofluoromethane sold by E. I. duPont de Nemours & Co.            .sup.7 Organic tin catalyst sold by Witco Chemical Corp.                       .sup.8 Potassium octoate in glycol sold by M&T Chemical Co.                    .sup.9 Polymeric isocyanate sold by Mobay Chemical Corp.                       .sup.10 Polymeric isocyanate sold by Upjohn Co.                           

We claim:
 1. A compound comprising a phenol which is substituted by a phosphorus containing structure having the formula: ##STR15## in which R is an alkanol or polyoxyalkylene group, and R' is an alkyl group, said compound being a polyol.
 2. The compound of claim 1 in which the phenol is nonylphenol, phenol, isopropyl phenol, a cresol, dodecylphenol or Bisphenol A.
 3. The compound of claim 1 as the product of a Mannich reaction.
 4. A compound comprising a phenol which is substituted by a phosphorus containing structure having the formula: ##STR16## in which R is an alkanol or polyoxypropylene group, and R' is a methyl or ethyl group, said compound being a polyol.
 5. The compound of claim 4 in which the phenol is nonylphenol, phenol, isopropyl phenol, a cresol, dodecylphenol or Bisphenol A.
 6. The compound of claim 4 as the product of a Mannich reaction.
 7. A compound having the formula: ##STR17## 